alpha-[beta&#39;, beta&#39;-bis(dihydroxyphenyl)-diethylamino]-anthraquinones



3,337,589 ot-[p',,8-BIS(DIHYDROXYPHENYL)-DIETHYL- AMINOl-ANTHRAQUINONESElkan R. Blout, Belmont, and Myron S. Simon, Newton Center, Mass.,assignors to Polaroid Corporation, Cambridge, Mass., a corporation ofDelaware No Drawing. Continuation of application Ser. No. 181,800, Mar.22, 1962. This application Oct. 28, 1966, Ser. No. 591,392

2 Claims. (Cl. 260378) This application is a continuation of Ser. No.181,800, filed Mar. 22, 1962, now abandoned, which is acontinuation-in-part of our copending application Ser. No. 680,- 437,filed Aug. 26, 1957 (now US. Patent No. 3,047,386, issued July 31,1962).

This invention relates tochemistry and more particularly to compoundsuseful in photographic products, compositions and processes for thedevelopment of photosensitive silver halide elements.

It is one object of the present inventionto provide novel developingagents useful in processes and compositions for the development ofsilver halide emulsions.

Another object is to provide novel processes and compositions for thedevelopment of silver halide emulsions, in which the novel developingagent is capable of developing a latent image and imparting a reversedor positive colored image of said latent image to a superposedimagereceiving material.

Still another object is to provide novel products, processes andcompositions suitable for use in preparing monochromatic andmulti-chromatic photographic images.

A further object is to provide novel compounds which are useful asintermediates and color-providing materials.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the processes involving the severalsteps and the relation and order of one or more of such steps withrespect to each of the others, and the products and compositionspossessing the features, properties and the relation of elements whichare exemplified in the following detailed disclosure, and the scope ofthe application of which will be indicated in the claims.

The novel photographic developing agents of this invention possess theproperties of both dye and a developing agent; thus they may be referredto as dye developers. The nature of these dye developers will bedescribed hereinafter.

The photographic processes and compositions disclosed herein areparticularly useful in the treatment of a latent image present in aphotosensitive element, such as an exposed silver halide emulsion,whereby a positive dye image thereof may be imparted to another element,herein referred to as an image-carrying or image-receiving element.

US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers,discloses diffusion transfer processes wherein a photographic negativematerial such as a photographic element comprising an exposed silverhalide emulsion layer containing a latent image, is processed, using adye developer, to impart to an image-receiving element a reversed orpositive dye image of said latent image by permeating into said emulsionlayer a suitable liquid processing composition and bringing saidemulsion layer into superposed relationship with an appropriateimagereceiving layer. It is an object of this invention to provideadditional dye developers suitable for use in such processes.

In carrying out the photographic transfer process, a photosensitiveelement containing a silver halide emulsion is exposed and wetted with aliquid processing composition, for example, by immersing, coating,spraying, flow- United States Patent Q ing, etc., in the dark, and thephotosensitive element superposed, prior to, during or after Wetting, ona sheetlike support element, which may be utilized as an image-receivingelement. In a preferred embodiment, the photosensitiv e element containsa layer of dye developer, and the liquid processing composition isapplied to the photosensitive element in a uniform layer as thephotosensitive element is brought into superposed position with animage-receiving element. It is also within the scope of this inventionto apply the liquid processing composition prior to exposure, inaccordance with the disclosure in the copending application of Edwin H.Land, Ser. No. 498,672, filed Apr. 1, 1955 (now U.S. Patent No.3,087,816, issued Apr. 30, 1963). The liquid processing compositionpermeates the emulsion to provide a solution of dye developersubstantially uniformly distributed therein. As the latent image isdeveloped, the oxidation product of the dye developer is immobilized orprecipitated in situ with the developed silver, thereby providing animagewise distribution of unoxdized dye developer dissolved in theliquid processing composition. This immobilization is apparently, atleast in part, due to a change in the solubility characteristics of thedye developer upon oxidation, and especially as regards its solubilityin alkaline solutions. It may also be due, in part, to a tanning etfecton the emulsion by the oxidized developing agent. At least part of thisimagewise distribution of unoxidized dye developer is transferred, byimbibition, to a superposed image-receiving layer or element, saidtransfer substantially excluding silver or oxidized dye developer. Undercertain circumstances, the layer of the liquid processing compositionmaybe utilized as the image-receiving layer. The latter element receives adepthwise diffusion, from the emulsion, of unoxidized dye developerwithout appreciably disturbing the imagewise distribution thereof toprovide a reversed or positive, colored image of the developed image.The image-receiving element may contain agents adapted to mordant orotherwise fix the diffused, unoxidized dye developer. If the color ofthe diffused dye developer is affected by changes in the pH of theimage-receiving element, this pH may be adjusted in accordance withwell-known techniques to provide a pH affording the desired color.Imbibition periods of approximately one minute have been found to givegood results, but this contact period may be adjusted where necessary tocompensate for variations in temperature or other conditions. Thedesired positive image is revealed by stripping the image-receivingelement from the photosensitive element at the end of the imbibitionperiod.

The dye developers of this invention may be utilized in thephotosensitive element, for example in, on or behind the silver halideemulsion, or they may be utilized in the image-receiving element or inthe liquid processing composition. In a preferred embodiment, a coatingor layer of the dye developer is placed behind the silver halideemulsion, i.e., on the side of the emulsion adapted to be located mostdistant from the photographed subject when the emulsion is exposed andpreferably also adapted to be most distant from the image-receivingelement when in superposed relationship therewith. Placing the dyedeveloper behind the emulsion layer, as in the preferred embodiment, hasthe advantage of providing increased contrast in the positive image, andalso minimizes any lightfiltering action by the colored dye developer.In this preferred embodiment, the layer of dye developer may be appliedby using a coating solution containing about 0.5 to 8%, by weight, ofthe dye developer. Similar concentrations may be used if the dyedeveloper is utilized as a component of the liquid processingcomposition, concentrations as low as 0.2% in the liquid processingcomposition being suitable in certain instances.

The liquid processing composition above referred to comprises at leastan aqueous solution of an alkaline compound, for example, dieth'ylamine,sodium hydroxide or sodium carbonate, and may contain the dye developer.In some instances, it may contain a small amount of a conventionalaccelerating silver halide developing agent. If the liquid processingcomposition is to be applied to the emulsion by being spread thereon,preferably in a relatively thin, uniform layer, it may also include aviscosityincreasing compound constituting the film-forming material ofthe type which, when said composition is spread and dried, will form arelatively firm and relatively stable film. A preferred film-formingmaterial is a high molecular weight polymer such as a polymeric,water-soluble cellulose ether inert to an alkali solution, as forexample, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.Other film-forming materials or thickening agents whose ability toincrease viscosity is substantially unaffected when left in solution fora long period of time may also be used.

The novel dye developer compounds of this invention are anthraquinoneswhich have at least one and not more than two of the nuclear carbonatoms in the 1-, 4-, and S-positions of the anthraquinone nucleus linkedto a group of the formula:

32 (ilH-R Y \CH-CH2-Y wherein each Y is a dihydroxyphenyl silver halidedeveloping radical; R is a hydrogen, methyl or ethyl group; R is ahydrogen or alkyl group and preferably an alkyl group containing no morethan 5 carbon atoms, such as methyl, ethyl, propyl, etc., and R is analkylene group and preferably an alkylene group containing no more than5 carbon atoms, such as methylene CH ethylene CH CH propylene -CH CH CHisopropylene -oH,-,oH

CH3 1,4-butylene CH CH CH CH 1,2-butylene -oH,oH-

etc. groups.

It should be understood that when desired the carbon atoms of theanthraquinone nucleus which are not substituted by tertiary aminoradicals set forth above may be substituted by other incidentalsubstituents which are commonly found thereon. As examples of suchsubstituents mention may be made of alkyl, alkoxy, aryl, aryloxy, amino,halogen, hydroxy nitro, sulfo, carboxyl, cyano, sulfonamido andcarboxamido groups.

Novel dye developer compounds within the scope of this invention may bemore specifically set forth by the formula:

wherein each X is a hydrogen, alkyl, alkoxy, halogen, or nitro group ora radical, provided that at least one X and not more than two Xs aresaid radical is substituted in the 1 position of the anthraquinonenucleus and each Y is a p-dihydroxyphenyl group. Such compounds may bepresented by the formula:

Y is defined above as a dihydroxyphenyl silver halide developingradical. This terminology is quite definite in scope and refers to thewell-known photographic equivalents, i.e., the orthoandpara-dihydroxyphenyl radicals. It should be understood that, whendesired such orthoand para-dihydroxyphenyl groups may be furthersubstituted by other substituents which do not interfere or whichenhance the silver halide developing power of such radicals. As examplesof such substituents, mention may be made of halogen, alkyl and alkoxy.

The preferred dye developer of this invention is 1 [a methyl 5,5 bis(2',5' dihydroyphenyl) diethylamino] -5-nitro-anthraquinone.

The novel compounds of this invention may be prepared by condensing asuitable halogen or nitro-substituted anthraquinone with an amine of thestructure or a salt thereof, wherein Y, R R and R have the same meaningas above. As examples of suitable halogen and nitro-substitutedanthraquinones useful in preparing the dye developers of this invention,mention may be made of 1 nitroanthraquinone, 1,5 dinitroanthraquinone,1,8- dinitroanthraquinone, l-chlo-roanthraquinone and1,4-dichloroanthraquinone and of the sulfo-, carboxyl-, amino-, cyano-,nitro-, hydroxy-, halogen-, alkyl-, aryl-, alkoxy aryloxy,sulfonamidoand carboxamido substituted derivatives of these compounds.

Amines within Formula A may be prepared by the processes disclosed inUS. Patent 2,949,359 of Elkan R. Blout, Milton Green and Myron S. Simon,issued Aug. 16, 1960.

As an example of such an amine, mention may be made of:

OH OH CHzCHzNH-CHCH Example 1 0.75 gm. of 1,5-dinitroanthraquinone, 4.8gms. of amethyl 5,,6 bis (2,5 dihydroxyphenyl) diethylamine hydrobromideand 1.06 grns. of sodium acetate are dissolved in 8 cc. of pyridine and1 cc. of water. The solution is deaerated with nitrogen and refluxed forfive hours. The solution becomes magenta almost immediately and thenturns red after about a half hour. At the end of the reflux period, theproduct is precipitated with dilute hydrochloric acid, filtered, andwashed with water. The precipitate is purified by dissolving it inmethyl cellosolve and precipitating with water. After repeating thepurification step two additional times,1-[a-methyl-B,fi-bis-(2,5'-dihydroxyphenyl) diethylamino] 5 nitroanthraquinone, exhibiting an absorption maximum, in dimethylfonmamide,at 500 m e=13,500, is obtained, possibly mixed with unreacted1,S-dinitro-anthraquinone.

The following nonlimiting example illustrates the use of a dye developerin the processes of this invention.

Example 2 aqueous liquid processing composition comprising:

Percent Sodium carboxymethyl cellulose 4.5 Potassium bromide 0.21-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 2.0

between said photosensitive element and an image-receiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose acetate-coated barytapaper which has been coated with a 4% solution of N-methoxy-methylpolyhexamethylene adipamide in isopropanol. After an imbibition periodof approximately one minute, the imagereceiving element is separated andcontains a salmon pink positive image of the photographed subject.

It should be noted that certain dye developers are sensitive to pHchanges. Since the dye developer is rendered effective by solution in anaqueous alkaline processing composition, it accordingly is necessary toassure that the environment in which the transferred and unreacted dyedeveloper is deposited has or is capable of attaining the requisite pHaffording the desired color to the diffused dye developer. This may beaccomplished by use of a volatile basic compound such as diethylamine inthe liquid processing composition. If sodium hydroxide is utilized inthe processing liquid, it becomes carbonated after processing and bycontact with the air and. this is effective to provide the desired pHchange. Further control of the pH of the transferred and unreacted dyedeveloper may be had by utilizing an image-receiving element which isdiflicultly penetrable by alkali, for example an appropriate nylon suchas N-methoxymethyl polyhexamethylene adipamide, or by the use of areceiving element in which an acid or an acid-forming compound, e.g.,oleic acid, has been incorporated.

It will be noted that the liquid processing composition may, and in theabove example does, contain an auxiliary or accelerating developer, suchas N-methyl-p-aminophenol sulfate, 2,4-diaminophenol hydrochloride,benzylaminophenol, or a 3-pyrazolidone, such as 1-phenyl-3- pyrazolidone(Phenidone). The preferred auxiliary developer is1-phenyl-3-pyrazolidone. This auxiliary developer serves to accelerateand possibly initiate the action of the dye developer. A portion of thedye developer may be oxidized by an energy transfer reaction withoxidized auxiliary developer.

The dye developers of this invention may be used also in conventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films, plates or papers to obtain black-and-white,monochro. matic or toned prints or negatives. By way of example, adeveloper composition suitable for such use may comprise an aqueoussolution of approximately 1 to 2% of the dye developer, 1% sodiumhydroxide, 2% sodium sulfite and 0.05% potassium bromide. Afterdevelopment is completed, any unreacted dye developer is washed out ofthe photosensitive element, preferably with an alkaline washing mediumor other medium in which the unreacted dye developer is soluble. Theexpression toned is used to designate photographic images wherein thesilver is retained with the precipitated dye, whereas monochromatic isintended to designate dye images free of silver.

It should be noted that the dye developers of this invention areself-suflicient to provide the desired color image and do not dependupon coupling reactions to produce the desired color. They thus providea complete departure from conventional photographic color processes inwhich the color is produced by a coupling reaction involving theoxidized developing agent.

It should be noted that it is within the scope of this invention to usemixtures of dye developers to obtain a desired color.

It will be apparent that, by appropriate selection of theimage-receiving element from among suitable known opaque and transparentmaterials, it is possible to obtain either a colored positive reflectionprint or a colored positive transparency. Likewise, the inventiveconcepts herein set forth are adaptable for multicolor work by the useof special photographic materials, for example, film materials of thetype containing two or more photosensitized elements associated with anappropriate number of imagereceiving elements and adapted to be treatedwith one or more liquid processing compositions, appropriate dyedevelopers suitable to impart the desired subtractive colors beingincorporated in the photosensitized elements or in the liquid processingcompositions. Examples of such photographic materials are disclosed inthe US. Patent No. 2,647,049 to Edwin H. Land.

The inventive concepts herein set forth are also adaptable for theformation of colored images in accordance with the photographic productsand processes described and claimed in US. Patent 2,968,554, issued toEdwin H. Land on Jan. 17, 1961, and the copending application of EdwinH. Land and Howard G. Rogers, Ser. No. 565,135, filed Feb. 13, 1956.

In the preceding portions of the specification, the expression color hasbeen frequently used. This expression is intended to include the use ofa plurality of colors to obtain black, as well as the use of a singleblack dye developer.

Since certain changes may be made in the above products, compositionsand processes without departing from the scope of the invention hereininvolved, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative and not-in a limitingsense.

What is claimed is:

1. A tertiary amine compound of the formula X X ll wherein at least oneX and not more than two Xs are of the formula each Y is selected fromthe group consisting of orthoand para-dihydroxyphenyl groups; R isselected from the group consisting of hydrogen, methyl and ethyl groups;R is selected from the group consisting of hydrogen and an alkyl groupcontaining no more than five carbon atoms; R is an alkylene groupcontaining not more than five carbon atoms; the remaining Xs beingindependently selected from the group consisting of hydrogen, nitro andhalogen.

2. l [a methyl [3,5' bis (2,5' dihydroxyphenyl)- diethylamino]-5-nitro-antraquinone.

No references cited.

LORRAINE A. WEINBERGER, Primary Examiner.

H. WEGNER, Assistant Examiner.

1. A TERTIARY AMINE COMPOUND OF THE FORMULA